Polymerizable unsaturated methylene compound and resin comprising polymers thereof



Patented Apr. 20, 1943 POLYMERIZABLE UNSA'IUBATED METHYL-.

ENE COMPOUND AND RESIN COMPRISING POLYMERS THEREOF 'Lorlng Coes, Jr., Brooklleld, and Carl E. Barnes,

Worcester, Mass., assignors, by mesne assignments, to E. I. an Point de Nemours 3; Company,

Wilmington, Del., a corporation of Delaware No Drawing.

4 Claims.

This invention relates to polymerizable unsaturated methylene compounds and resins comprising polymers thereof.

Various polymerizable unsaturated methylene Application February 28, 1939, Serial No. 258,958

In accordance with one phase of our invention, we propose to make the monomeric acrylic and methacrylic acid derivatives of various aromatic amines capable of polymerization, such as the compounds containing the group 5 ortho', metaand para-phenylene diamines,

R ortho-, metaand para-toulidines, toluylene di 1 1 amine, alpha and beta naphthyiene amines, om=o naphthalene diamines, amino derivatives of diln whi R y be hydrogen or a t y o p, phenyl, as well as other primary or secondary such as m thyl m t yla polymerize to form aromatic amines. Another phase of this int ansp t d t y y have the Wrong vention resides in the polymerization of such index of refracti n d sp Value o l monomers and'the formation of synthetic resins other characteristics desired for making optical of nu r rti A further feature is t bo s. su h as len It i h w ver. feasible to formation of resins of particular use as optical modify the properties of such polymerized b 5 bodies, by polymerizing various unsaturated substances by the addition of a suitable agent methylene compounds serving as base substances, before P y i i n thereof, and particularly defined below, with methacryl aniline and the y p lymerizin a s le t d base su st n e in the other acrylic and methacrylic acid derivatives of presence of a polymerized orpolymerizable modit amin fying agent having e required opti al p op These derivatives may be made from numerous ties and capa e of forming an optic l bo y amines capable of forming useful polymers. As therewith. an example, we maqe make a polymerizable sub- We have discovered that h yl n li stance from ortho-phenylene diamine, such as heretofore made in the mon meric for may the di-N-methacryl derivative thereof, which is be p ymerized and made to servees a modify considered to have the structural formula agent to vary the refractive index and other H 0 on. properties of such base substances. We have also I ll 6 discovered that other and hitherto unknown acrylic and methacrylic acid derivatives of the aromatic amines may be made as monomeric 3U fsubstances and polymerized to form useful resins ii 0 In by themselves. and that these P ymers will also As an example of the secondary aromatic amines serve as modify n a n s f t r polymerized of the above 'group, we may use N-alkyl or N-aryl unsat ated et y o pound a d pertieuaromatic amines, such as N-methyl aniline or N- larly for making transparent resins capable of use pheny] l asoptical bodies. These compounds may be made by the same One object of the invention is therefore to general procedure. For example, the di N P vi e optical bodies of required chara teris methacryl derivative of ortho-phenylene diamine by modifying the properties of suitable base submay be made by gradually' adding 25 grams of nce y means of such polymerizable deriv 40 ortho-phenylene diamine to 80 cc. of methacrylic tives. anhydride, with cooling. After all of theamine Further objects are to provide new and useful has dissolved, the solution is allowed to stand at monomeric and polymeric acrylic and methacrylic room temperature for two hours and then poured acid derivatives of the aromatic amines, and to into water. The precipitate may then be filtered provide polymerizable substances which are capaoff and recrystallized from methyl alcohol. The ble of forming useful resins and of serving as product as thus made crystallizes from methyl modifying agents for other polymers. alcohol as colorless transparent needles and has A still further object is to make a resin of a a melting point of 124 C. It polymerizes to polymerized unsaturated methylene base subform a hard brittle transparent resin having a stance modified by a polymerizable, aromatic refractive index of 1.61. The monomeric subamine derivative which is capable of providing. stance analyzes to give 11.34% of nitrogen, required optical properties, together with a, furwhereas the calculated amount according to the ther polymerizable substance which imparts deformulais 11.49. sired physical properties thereto. Further ob- The various monomeric substances of the above Jects will be apparent in the following disclosure. group are capable of polymerizing with the aid of heat and if desired, a catalyst, such as benzoyl peroxide, to form transparent resins.- These substances are particularly useful for the purpose of modifying the refractive index and other properties of various base substances selected from the group of the polymerizable unsaturated mono-methylene compounds. when they are interpolymerized from a mixture of the monomeric liquids.

Suitable base substances capable of being used with these polymerizable amine derivatives are:

1. Derivatives of acrylic acid and methacrylic acid, such as their esters, amides and halides.

2. Vinyl esters.

3. Polymerizable substituted ethylenes.

4. Mono-vinyl and substituted mono-vinyl ketones.

5. Mono-vinyl ethers.

6. Mono-vinyl and substituted mono-vinyl a1- dehydes.

While many other base substances may be used within the scope of our invention, the following are given as examples of those substances in the above groups which are usable with our modifying agents:

1. The esters of acrylic acid and methacrylic acid comprise methyl, ethyl, isopropyl and terbutyl acrylates and methacrylates and other alkyl esters of these acids, as well as the mono esters of the polyhydric alcohols. They also comprise aryl esters, such as phenyl or benzyl acrylate or 'methacrylate or paracyclohexylphenyl acrylate or methacrylate. Acryl and methacryl amides and chlorides may also be used.

2. The vinyl esters comprise vinyl acetate, propionate, butyrate, etc.

3. The preferred substituted ethylenes are styrene, furyl ethylene, vinyl chloride and nitroethylene.

4. The preferred ketones comprise methyl vinyl ketone and isopropenyl methyl ketone.

. 5. The mono-vinyl ethers comprise methyl vinyl ether, phenyi vinyl ether and similar substances.

6. Examples of the aldehydes are acrolein and alpha methyl acrolein.

Useful interpolymers may be made from any one of these base substances with any one of the modifying agents which we have discovered,

as well as with methacryl aniline, and we may choose any base substance and any modifying agents of these above groups which are compatible with one another and which are proportioned in miscible amounts so that they may be ccpolymerized with molecules of both substances in the same chain. Also, for certain purposes, we may first polymerize onesubstance and then polymerize the other in its presence, provided the previously polymerized substance is soluble in the other in both its monomeric and polymeric form.

As an example of this phaseof our invention, methyl methacrylate copolymerized with of methacryl aniline forms a resin of high transparency having a refractive index of about 1.52. The copolymer has a Rockwell hardness of 69 as comparedwith a hardness of about to for the commercial methyl methacrylate. Hence, these two substances may be used in various proportions to give different refractive indices and/or hardness characteristics varying between those of the two chosen materials, depending upon the proportions used. The refractive index is proportional to the amount of modifying agent used. For example, the index of methyl methacrylate is about 1.49 and the index of methacryl aniline is about 1.615; hence these vary by 0.125

so that each 10% of methacryl aniline employed will give an increase of index of about 0.0125

, over that of the methyl methacrylate. The other optical properties of the body may be likewise varied. It will be noted that the dispersion of the single polymerized modifying agent, or of the copolymer therewith with one of the base substances, is materially different from that of a silicate glass having the same refractive index. Hence, by a suitable choice of materials'in these two groups, one may produce a body having a chosen index and a desired dispersion value; and at the same time the hardness characteristics of the body may be suitably modified by copolymerization with a cross linking agent or hardness improving polymer as herein defined.

The acrylic and methacrylic acid derivatives of the poly-amines contain a plurality of the unsaturated methylene groups and thereby are capable of acting as cross linking agents when interpolymerized with the mono-methylene compounds used as base substances. Hence these poly-methylene compounds may serve to increase the hardness or to decrease the solubility or to raise the softening point of the resin formed of the linear chain base substance when interpolymerized therewith. The mono-amines contain only a single =CH2 group and polymerize only in linear chain formation, hence they may be used to modify the refractive index without materially affecting the solubility, hardness or fusibility of the resin; while the polymethylene compounds may be employed to change the index as well as to modify these other physical characteristics.

As further hardness modifying agents, we may use any polymerizable substance comprising a cross linking agent or a polar compound or other group which will impart desired characteristics to the copolymer. The cross linking agents are those compounds containing two or more polymerizable unsaturated methylene groups per molecule which are compatible and miscible with the base substance and are capable of copolymerizing therewith. Examples of such cross linking agents are the polyhydric alcohol esters of acrylic and methacrylic acids, also the anhydrides, nitriles, and vinyl, allyl and substituted allyl esters of these acids. Examples of the polyhydric alcohols are the hypothetical ethylidene glycol, ethylene glycol, glycerol, pentaglycerol, and various other polyhydric alcohols capable of forming esters with these acids and their homologues. Other desirable cross linking agents are divinyl benzene and divinyl ketone and homologues.

We may also use a modifying agent which improves the hardness characteristics of the body due to the presence of polar substituents, such as carboxyl or amino groups. For example, acrylic acid and methacrylic acid are believed to act as if the carboxyl groups in adjacent chains attract each other, thus raising the softening point and increasing the hardness of the copolymer.

Hence, we may choose an amine derivative to ive a proper index of refraction and, if the hardness is not right for a given purpose, this may be improved by the use of a further modifying agent, although many of the amine derivatives increase the hardness to some extent.

By a suitable choice of base substance, index we may make copolymersot various utilities in the optical and other fields. These substances may besmixed together in their monomeric form in miscible proportions and wherein the amounts selected give the properties desired. The mixture may then be subjected to heat and with or without a catalytic agent to form the resin.

If an optical body is to be made, the pro portions of the mixture are to be such as to form one which is not cracked or so full of strains that it may crack during use and which may be shaped under pressure by a high temperature molding operation or which may be cast to a rough'shape and thereafter ground and polished by a standard optical grinding operation to provide a true optical surface. A resin which has become cracked or is otherwise so imperfect that it will not transmit light properly to form a clear optical image is 01 little value in the optical field and the substances are, therefore, to be proportioned to form a useful body.

It will be understood that the above description 0! this invention is to be considered as illustrative of the general principles as well as specific applications thereof and that it is not to be construed as limitations thereon except as defined in the following claims.

We claim: 7

l. Ortho-phenylene diamine in which both of the amino groups contain as a substituent the group.

3 2. A synthetic resin obtained by polymerizing ortho-phenylene diamine in which both of the amino groups contain as a substituent the 3. An aromatic diamine from the group consisting of the phenylene, toluylene, diphenyl, and naphthalene diamines, in which all of the amino groups contain as a substituent a group from the class consisting of i O CH: O

' groups.

4. A synthetic resin obtained by polymerizing an aromatic diamine from the group consisting of the phenylene, toluylene, diphenyl, and naphthalene diamines, in which all 0! the amino groups contain asia substltuent a Group fromthe class consisting of LORING GOES, JR. CARL E. BARNES. 

